Water sheeting zwitterionomeric aminofunctional siloxanes

ABSTRACT

A polish formulation containing as components at least one member selected from the group consisting of waxes, solvents, surfactants, thickening agents, abrasives, dyes, odorants, and other ingredients normally used in making polishes, and as an improvement incorporating a composition which is the reaction product of an acid anhydride and an aminofunction siloxane. The resulting zwitterionic aminofunctional siloxane can, if desired, be further reacted with a strong acid to provide an equilibrium of the zwitterion and a conjugate acid base pair of the zwitterion and the acid. The invention also includes a method of sheeting water on a surface with the polish, a method of making an aminofunctional siloxane zwitterionomer, and an aminofunctional zwitterionomeric siloxane compound which is the reaction product.

This is a divisional of co-pending application Ser. No. 07/293,842 filedon Jan. 5, 1989, now U.S. Pat. No. 4,898,614, patented Feb. 6, 1990.

BACKGROUND OF THE INVENTION

This invention relates to a polish formulation including a zwitterionicaminofunctional siloxane which imparts to the surface containing thepolish a film forming capacity which functions to sheet water cominginto contact with the surface rather than to bead the water as has beenthe case with prior formulations.

Polishes are used to produce a glossy finish on a surface as well as toprolong the useful life of the surface. The gloss provided by the polishis the result of components in the polish which leave a coating and thatfunction to smooth and clean the surface. Floor polish, furniturepolish, and shoe polish, rely upon a deposited film. Car and boat polishformulations result in a glossy and protective film and containabrasives for removing weathered paint and soil as well as old built-uppolish. Metal polish contains ingredients for abrasive smoothing of thesurface being treated and for surface cleaning, as well as componentthat function to remove and retard the build-up of tarnish.

Motor vehicle polish is formulated in order to remove road film andoxidized paint, and to provide a continuous glossy film which resistswater and its removal by water and car wash detergents. Such vehiclepolishes contain several major functional ingredients including anabrasive. The abrasive, however, must be mild enough to avoid scratchingof the painted surface, and representative of such mild acting materialsare, for example, fine grades of aluminum silicate, diatomaceous earth,and various silicas. Straight and branched chain aliphatic hydrocarbonsare employed to facilitate the detergency of the polish against oilbased traffic soils and debris, and provide the solvency characteristicsnecessary in the production of a stable formulation. These hydrocarbonsalso control the drying rate of the formulation. Wax constitutes anotherpolish ingredient and is one of the two film forming materials in thepolish. The wax is spread and leveled and produces a high lusterfollowing buffing of the surface. Blends of soft and hard wax are oftenemployed in order to facilitate ease of buffing and the durability ofthe polish against environmental antagonists. Exemplary waxes areparaffin wax, microcrystalline petroleum wax, carnauba wax, candellavegetable wax, montan coal derived was, and synthetic polymeric waxessuch as oxidized polyethylene.

Silicone materials are included in polishes as the other film formingingredient. Such silicone materials also function as lubricants foreasing the application of the polish as well as its buffing, and act asrelease agents for dried abrasive. The silicone materials spread easilyand provide a uniform high gloss and with it water repellency. Suchmaterials typically are dimethylsilicones, however, aminofunctionalsilicone products are becoming more prevalent. The aminofunctionalproducts result in films having increased resistance to removal from thesurface by detergents and the environment believed to be the result oftheir ability to plate out on a painted surface and to crosslink andbond to that surface.

A car polish may also contain an emulsifier, a thickener, and astabilizer, for the production of a homogeneous stable product ofdesired consistency. Such polishes may be solid in form, semisolid,presoftened, or liquid. The polish, for example, can be solvent based oran emulsion, and in either case is a liquid, semi-solid or solid inconstruction. Typically, liquid emulsions include ten to fifteen weightpercent of an abrasive, ten to thirty weight percent of solvent, two tofifteen weight percent of a silicone material, and up to about fourweight percent wax. In an emulsion paste formulation, the wax ingredientis increased in level from three to twenty-five weight percent.

In U.S. Pat. No. 3,956,353, issued May 11, 1976, there is disclosed thereaction product of an aminofunctional silane and a cyclic acidanhydride. These products are limited, however, to vinyl benzylfunctional amines whereas the materials of the present invention differin the amine group, and do not require such a substitution. Suchproducts further are not disclosed to be useable in a polish formulationas such, but are aqueous or alcohol coupling agent compositions, incontrast to the polish composition disclosed in the present invention.Polishes, it should be noted, require polymers with significant dimethylcharacter for solubility, as are the aminofunctional siloxanezwitterions of the present invention. The reaction products in U.S. Pat.No. 3,956,353, however, are low molecular weight monomer materials.Polish formulations containing silicone materials are disclosed in U.S.Pat. No. 3,508,933, issued Apr. 28, 1970, in U.S. Pat. No. 3,836,371,issued Sept. 17, 1974, and in U.S. Pat. No. 3,890,271, issued June 17,1975. While these silicone materials are characterized as beingaminofunctional siloxanes, they are not zwitterionomers as are thecompositions of the present invention, and it is not believed to beknown to employ zwitterionomers in polish formulations. What appears tobe a zwitterion in a polish in Japanese Publication No. 8029/80 isactually an amido acid. Such acids are low molecular weight hard solidsin contrast to the high molecular weight fluids of the presentinvention. Further, the function of such amido acids is to increase theluster or shine of a polish, rather than to cause water to sheet as inthe present invention. Zwitterionomers are not new as exemplified byU.S. Pat. No. 4,525,567, issued June 25, 1985, to Campbell et al,however, the zwitterionomers of Campbell et al. are characterized asbeing sultone based zwitterionomers whereas the zwitterionomers of thepresent invention are sulfur free amine cyclic-anhydride basedzwitterionomers in contrast thereto. Further, the zwitterionomers of thepresent invention are lactone free in contrast to Campbell et al. Afurther distinction exists between the instant invention and that ofCampbell et al, in that in Campbell et al, there is disclosed a low costprocess of making the zwitterions by combining OH endblockedpolydimethylsiloxane, a functional silane, and an acid catalyst. In thepresent invention, however, the zwitterionomers can be prepared fromfully-premade aminofunctional siloxane polymers which are not siliconfunctional. As such, the compositions of the present invention providenew and unique advantages over typical prior art polish formulationswhich will become apparent hereinafter.

SUMMARY OF THE INVENTION

This invention relates to a polish formulation containing as componentsthereof at least one member selected from the group consisting of waxes,solvents, surfactants, thickening agents, abrasives, dyes, odorants, andother ingredients normally used in making polishes. The improvementincludes incorporating therein a composition which is the reactionproduct of a cyclic acid anhydride and an aminofunctional siloxaneselected from the group consisting of (A) a blend or reaction product ofa hydroxyl endblocked polydimethylsiloxane having a viscosity in therange of about 10 to 15,000 cs at twenty-five degrees centigrade, and asilane selected from the group consisting of those having the generalformulae R"_(n) (R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n) (R'O)_(3-n)SiRNHCH₂ CH₂ NH₂ wherein R"' is a hydrogen atom or a methyl radical, R"is a monovalent hydrocarbon radical free of aliphatic unsaturation andcontains from one to six carbon atoms, n has a value of from zero totwo, R' is an alkyl radical containing from one to four carbon atoms,and R is a divalent hydrocarbon radical free of aliphatic unsaturationand contains three to four carbon atoms, (B) a blend or reaction productof a hydroxyl endblocked polydimethylsiloxane having a viscosity in therange of about 10 to 15,000 cs at twenty-five degrees centigrade, asilane selected from the group consisting of those having the generalformula (R₁ O)₃ --SiR₂ NHR₃ and (R₁ O)₃ --SiR₂ NHCH₂ CH₂ NH₂ wherein R₁is an alkyl radical containing from one to four carbon atoms, R₂ is adivalent hydrocarbon radical free of aliphatic unsaturation and containsfrom three to four carbon atoms, and R₃ is selected from the groupconsisting of the hydrogen atom and the methyl radical, and a silanehaving the general formula X₃ SiZ wherein X is selected from the groupconsisting of alkoxy and acyloxy radicals containing from one to fourcarbon atoms, and Z is nonhydrolyzable radical selected from the groupconsisting of hydrocarbon radicals, halogenated hydrocarbon radicals,and radicals composed of carbon, hydrogen, and oxygen atoms, wherein theoxygen atoms are present in hydroxyl groups, ester groups, or etherlinkages, there being from one to ten carbon atoms in the Z radical, and(C) a blend or reaction product of a polydimethylsiloxane having aviscosity in the range of about one to 15,000 cs at twenty-five degreescentigrade, and a silane selected from the group consisting of thosehaving the general formulae R"_(n) (R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n)(R'O)_(3-n) SiRNHCH₂ CH₂ NH₂ wherein R"' is a hydrogen atom or a methylradical, R" is a monovalent hydrocarbon radical free of aliphaticunsaturation and contains from one to six carbon atoms, n has a value offrom zero to two, R' is an alkyl radical containing from one to fourcarbon atoms, and R is a divalent hydrocarbon radical free of aliphaticunsaturation and contains three to four carbon atoms. (C) above is aspecific species and a trimethylsilyl endblocked aminofunctionalsiloxane produced by incorporating conventional trimethylsilylfunctional silanes or siloxanes into the aminofunctional siloxanes.

In a specific embodiment of the present invention, the acid anhydride isselected from the group consisting of succinic anhydride, maleicanhydride, phthalic anhydride, and carbon dioxide. The reaction productis an aminofunctional siloxane zwitterion having the structural formula:##STR1## where Me is methyl, x is an integer of from about forty toabout four hundred, y is an integer of from about one to about twenty,and R₄ is ethylene, vinylidene, or phenylene. x is preferably 188 and yis ten.

The zwitterionic aminofunctional siloxane can, if desired, be furtherreacted with a strong acid resulting in an equilibrium of the zwitterionand a conjugate acid base pair of the zwitterion and the acid; for whichthe extent of conjugate acid base pair formation depends upon the pKa ofthe strong acid and the dielectric strength of the solvent. In suchcase, the strong acid is selected from the group consisting ofhydrochloric, hydrobromic, hydriodic, nitric, perchloric, phosphoric,and organic acids. The organic acid is selected from the groupconsisting of acetic, propionic, butyric, valeric, caproic, benzoic,halo-substituted benzoic, and nitro-substituted benzoic. The conjugateacid base pair of the zwitterion and the strong acid has the structuralformula: ##STR2## where Me is methyl, x is an integer of from aboutforty to about four hundred, y is an integer of from about one to abouttwenty, A is an anion and the conjugate base of the strong acid, and R₄is ethylene, vinylidene, or phenylene. x again is preferably 188 and yis ten.

The invention is further directed to a method of sheeting water on asurface in which there is applied to the surface before the surface isexposed to water a polish formulation containing as components thereofthe ingredients enumerated above.

The invention is also directed to a method of making an aminofunctionalsiloxane zwitterionomer comprising reacting an acid anhydride with anaminofunctional siloxane selected from the group consisting of (A) and(B) as set forth and detailed above.

Still further, the present invention relates to an aminofunctionalzwitterionomeric siloxane compound which is a reaction product of anacid anhydride with an aminofunctional siloxane selected from the groupconsisting of (A) and (B) again as defined hereinabove.

It is therefore an object of the present invention to provide a new andnovel type of polish formulation particularly adapted for use on motorvehicles in which water coming into contact with such surfaces issheeted and drained away rather then being beaded and repelled as hasbeen the practice of prior art formulations in the past. A particularadvantage to this approach is that vehicles need not be washed followingevery period of rain as has been the case due to spots caused by thebeads. Instead, with the sheeting action of the compositions of thepresent invention, this disadvantage is overcome, and rain is sheetedaway from vehicle surfaces without leaving behind the unaestheticappearance of rings containing debris.

These and other features, objects, and advantages, of the hereindescribed instant invention, should become more apparent when taken inconjunction with the following detailed description thereof.

DETAILED DESCRIPTION OF THE INVENTION

A surfactant is a compound that reduces surface tension when dissolvedin a liquid. Surfactants exhibit combinations of cleaning, detergency,foaming, wetting, emulsifying, solubilizing, and dispersing properties.They are classified depending upon the charge of the surface activemoiety. In anionic surfactants, the moiety carries a negative charge asin soap. In cationic surfactants, the charge is positive. In non-ionicsurfactants, there is no charge on the molecule, and in amphotericsurfactants, solubilization is provided by the presence of positive andnegative charges linked together in the molecule. A zwitterion is aspecial category and is a molecule that exists as a dipolar ion ratherthan in the un-ionized form. The molecule is neutral overall but has alarge charge separation like an amino acid. Zwitterions are also knownas hybrid ions, and internal or intramolecular salts. In the case ofamino acids, they are electrolytes having separated weakly acidic andweakly basic groups. For example, while shown as H₂ N--R--COOH, inaqueous solution .sup.⊕ H₃ N--R--COO⁻ is the actual species where aninternal proton transfer from the acidic carboxyl to the basic aminosite is complete. The uncharged species has separate cationic andanionic sites but the positive and the negative ions are not free tomigrate. Thus, it is a complex ion that is both positively andnegatively charged. Alkyl betaines are also representative ofzwitterions and are a special class of zwitterion where there is nohydrogen atom bonded to the cationic site. Some silicones are alsozwitterions and it is this special category of silicone zwitterion towhich the present invention relates.

The zwitterionomeric aminofunctional siloxane compositions of thepresent invention may be prepared in accordance with the followingschematic: ##STR3##

It should be noted in the above schematic that formula (I) denotes anaminofunctional siloxane, formula (II) denotes the zwitterionomer of thepresent invention, and formula (III) indicates the conjugate acid basepair of the zwitterionomer and the strong acid (HA). Formula (I) isgenerically described as an aminofunctional siloxane selected from thegroup consisting of reaction products of (A) a blend or reaction productof a hydroxyl endblocked polydimethylsiloxane having a viscosity in therange of about 10 to 15,000 cs at twenty-five degrees centigrade, and asilane selected from the group consisting of those having the generalformulae R"_(n) (R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n) (R'O)_(3-n)SiRNHCH₃ CH₂ NH₂ wherein R"' is a hydrogen atom or a methyl radical, R"is a monovalent hydrocarbon radical free of aliphatic unsaturation andcontains from one to six carbon atoms, n has a value of from zero totwo, R' is an alkyl radical containing from one to four carbon atoms,and R is a divalent hydrocarbon radical free of aliphatic unsaturationand contains three to four carbon atoms, (B) a blend or reaction productof a hydroxyl endblocked polydimethylsiloxane having a viscosity in therange of about 10 to 15,000 cs at twenty-five degrees centigrade, asilane selected from the group consisting of those having the generalformulae (R₁ O)₃ --SiR₂ NHR₃ and (R₁ O)₃ --SiR₂ NHCH₂ CH₂ NH₂ wherein R₁is an alkyl radical containing from one to four carbon atoms, R₂ is adivalent hydrocarbon radical free of aliphatic unsaturation and containsfrom three to four carbon atoms, and R₃ is selected from the groupconsisting of the hydrogen atom and the methyl radical, and a silanehaving the general formula X₃ SiZ wherein X is selected from the groupconsisting of alkoxy and acyloxy radicals containing from one to fourcarbon atoms, and Z is a nonhydrolyzable radical selected from the groupconsisting of hydrocarbon radicals, halogenated hydrocarbon radicals,and radicals composed of carbon, hydrogen, and oxygen atoms, wherein theoxygen atoms are present in hydroxyl groups, ester groups, or etherlinkages, there being from one to ten carbon atoms in the Z radical, and(C) a blend or reaction product of a polydimethylsiloxane having aviscosity in the range of about one to 15,000 cs at twenty-five degreescentigrade, and a silane selected from the group consisting of thosehaving the general formulae R"_(n) (R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n)(R'O)_(3-n) SiRNHCH₂ CH₂ NH₂ wherein R"' is a hydrogen atom or a methylradical, R" is a monovalent hydrocarbon radical free of aliphaticunsaturation and contains from one to six carbon atoms, n has a value offrom zero to two, R' is an alkyl radical containing from one to fourcarbon atoms, and R is a divalent hydrocarbon radical free of aliphaticunsaturation and contains three to four carbon atoms. Such compositionsare described in more or less detail in U.S. Pat. No. 3,508,933, issuedApr. 28, 1970, in U.S. Pat. No. 3,836,371, issued Sept. 17, 1974, and inU.S. Pat. No. 3,890,271, issued June 17, 1975. The preparation of thesecompositions and their use in polishes is also detailed in theaforementioned patents, the disclosures of which are incorporated hereinby reference thereto. Particular of such compositions prepared andfalling within the scope of the present invention is set forth in TableI.

                  TABLE I                                                         ______________________________________                                        Compound (I)      x       y                                                   ______________________________________                                        A                 45.75   2.25                                                B                 69.25   3.75                                                C                 96      2                                                   D                 188     10                                                  E                 295.9   2.1                                                 F                 400     8                                                   ______________________________________                                    

In the above schematic, the acid anhydride which is reacted withcompositions of formula (I) is selected from the group consisting ofsuccinic anhydride, maleic anhydride, phthalic anhydride, itaconicanhydride, or other cyclic anhydrides, and carbon dioxide, with thefirst named anhydride being the preferred material for use herein.

The resulting reaction product indicated by formula (II) in theforegoing schematic is an aminofunctional siloxane zwitterionomer havingthe structural formula: ##STR4## where Me is methyl, x is an integer offrom about forty to about four hundred, y is an integer of from aboutone to about twenty, and R₄ is ethylene, vinylidene, or phenylene. x ispreferably 188 and y is ten. The zwitterionic aminofunctional siloxaneof formula (II) is further reacted with a strong acid (HA) resulting inan equilibrium of the zwitterion (II) and a conjugate acid base pairindicated by formula (III) of the zwitterion (II) and the acid (HA)which depends upon the pKa of the strong acid and the dielectricstrength of the polish solvent. The strong acid (HA) is selected fromthe group consisting of hydrochloric, hydrobromic, hydriodic, nitric,perchloric, phosphoric, and organic acids, wherein the organic acid maybe one of the group consisting of acetic, propionic, butyric, valeric,caproic, benzoic, halo-substituted benzoic, and nitro-substitutedbenzoic. The resulting formula (III) as shown above of the conjugateacid base pair of the zwitterion (II) and the strong acid (HA) has thestructural formula: ##STR5## where again Me is methyl, x is a integer offrom about forty to about four hundred, y is an integer of from aboutone to about twenty, A is an anion, and R₄ is ethylene, vinylidene, orphenylene. x is preferably 188 and y is ten. This is a specificembodiment of the present invention, and is not a requirement that theconjugate composition (III) be formed in every instance. However, itshould be noted that where the conjugate (III) is formed, itnecessitates the presence in the formulation of an acid. The equilibriumreached between the zwitterionomer (II) and the conjugate (III) dependson the strength of the acid. Where the acid is strong, the conjugate(III) predominates. Where the acid is weaker, the zwitterionomerpredominates. As noted hereinbefore, such equilibrium depends upon thepKa of the strong acid and the dielectric strength of the solvent.Preferred solvents in accordance with the present invention are ethanoland toluene, for example.

The zwitterionic aminofunctional siloxane of formula (II) can also befurther reacted with a basic compound resulting in an equilibrium of thezwitterion (II) and a conjugate acid base pair indicated by formula (IV)of the zwitterion (II) and the basic compound which depends upon therelative pKa's of the base B and the basic sites of the zwitterion, andthe dielectric strength of the medium. The strong base is selected fromthe group consisting of organic amines, hydroxides, and lewis bases. Theresulting formula (IV) as shown below of the conjugate acid base pair ofthe zwitterion (II) and the basic compound has the structural formula:##STR6## where again Me is methyl, x is an integer of from about fortyto about four hundred, y is an integer of from about one to abouttwenty, BH is a cation and a protonated base, and R₄ is ethylene,vinylidene, or phenylene. x is preferably 188 and y is ten. This is aspecific embodiment of the present invention, and is not a requirementthat the conjugate composition (IV) be formed in every instance.However, it should be noted that where the conjugate (IV) is formed, itnecessitates the presence in the formulation of a basic compound such asdibutyl amine. The equilibrium reached between the zwitterionomer (II)and the conjugate (IV) depends on the strength of the base. Where thebase is strong, the conjugate (IV) predominates. Where the base isweaker, the zwitterionomer predominates. As noted hereinbefore, suchequilibrium depends upon the relative pKa'3 s of the strong base andzwitterion, and the dielectric strength of the solvent.

The aminofunctional siloxanes of the formula (I) type may also beprepared by an alternate method from that set forth in U.S. Pat. No.3,508,993, U.S. Pat. No. 3,836,371, and U.S. Pat. No. 3,890,271,aforementioned. In the alternate method, the starting material ismethyldimethoxy ethylenediaminoisobutyl silane of the formula:

    CH.sub.3 (CH.sub.3 O).sub.2 SiCH.sub.2 CH(CH.sub.3)CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2

This aminofunctional silane is distilled to an active concentration ofbetween about 95-99%. The silane is hydrolyzed with three moles of wateradded to one mole of the silane. The material is batch distilled atatmospheric pressure and at a temperature of about one hundred andthirty degrees centigrade. Methanol and residual water are then removedby vacuum stripping to yield an aminofunctional hydrolyzate. Theaminofunctional hydrolyzate is added to a mixture ofpolydimethylsiloxane of viscosity of 1.5 centistokes, a dimethylcyclicof the formula (Me₂ SiO)_(n) where n is three, four, or five, and acatalyst such as potassium hydroxide or potassium silanolate. Thismixture is equilibriated to a polymer by agitation and heat at about onehundred-fifty degrees centigrade. The mixture is cooled to about 80-90degrees centigrade or lower and the catalyst is neutralized by theaddition of acetic acid accompanied with mixing. The non-volatilecontent is increased by stripping of the volatiles under vacuum,followed by filtration of the material in a pre-coated plate and framefilter for the purpose of removing any haze in order to obtain aclarified product. A typical example of this procedure is set forthbelow.

EXAMPLE I

Into a round bottom flask was added 3,482,8 grams of a dimethylcyclic,439.2 grams of hydrolyzate, 78.4 grams of polydimethylsiloxane ofviscosity of 1.5 cs, and 38.3 grams of potassium silanolate catalyst.The contents of the flask were mixed under a nitrogen atmosphere fortwenty minutes. Heat was applied to the flask and the contents weremaintained at one hundred-fifty degrees centigrade for four hours. Themixtures was cooled to thirty-three degrees centigrade. The catalyst wasneutralized by the addition to the flask of 2.14 grams of acetic acid.The fluid was stirred overnight and filtered. The resulting product waswater clear and had a viscosity of 354 cs. The product contained fivemol percent amine and was identified as the material set forth in TableI where x=188 and y=10.

EXAMPLE II

Example I was repeated in order to produce an aminofunctional siloxaneof the formula (I) type. Zwitterionic aminofunctional siloxanesmaterials of the formula (II) type were obtained by separatelydissolving succinic anhydride in dimethoxyethane in order to provide aten weight percent solution of the anhydride. The succinic anhydride wasadded from a dropping funnel to the contents of the flask containing theformula (I) type aminofunctional siloxane, and the solution was heatedwith stirring at about fifty-five degrees centigrade and under anitrogen flow. The mixture was vacuum distilled at about twentymillimeters of mercury or less under a nitrogen atmosphere at onehundred-twenty degrees centigrade for about forty-five minutes or untilthe vapor reached about eighty degrees centigrade, to remove all of thedimethoxyethane and yielding the zwitterionomer. The resultingzwitterionomer was distilled to a solids content of about eighty-eightpercent. This example was repeated producing zwitterionomers havingamine mol percentages ranging from about 0.5 mol percent to about eightmol percent.

The zwitterionic aminofunctional siloxanes of the present invention,were formulated into polishes in place of the aminofunctional siloxanesemployed in U.S. Pat. Nos. 3,508,933, 3,836,371, and 3,890,271, causingwater coming into contact with the surface treated, to sheet rather thanto bead, as is conventional with prior art polish formulations. Thepolishes so formulated were applied both to actual vehicle surfaces aswell as test panels. Water contacting the treated surfaces sheeted waterand was noted by visual observation. Thus, prior art polishes lay down afilm, but the film is a water beading film, in contrast to the watersheeting film obtained when the zwitterionomeric compositions of thepresent invention are employed. In either case, a film is formed byapplying the polish to the surface to be treated and by rubbing in thepolish onto the surface and allowing the solvent to evaporate, leavingbehind the film. Inclusion of the zwitterionomers of the presentinvention, however, sheets the water, whereas omission beads the water.A distinct advantage of a water sheeting film is that, in contrast to afilm that beads the water, the water sheeting film will not collect dustand debris following a rain as do water beading films, which necessitatethat the surface be washed once more in order to remove the spots andrings caused by the water beading type of film. The water sheeting filmsof the present invention are of general application including suchsurfaces as motor vehicles, boats and navigable crafts, wood surfaces,plastic surfaces, and fiber surfaces. The films produce a high gloss,are durable, and are easy to apply.

It will be apparent from the foregoing that many other variations andmodifications may be made in the structures, compounds, compositions,and methods described herein without departing substantially from theessential features and concepts of the present invention.

Accordingly, it should be clearly understood that the forms of theinvention described herein are exemplary only and are not intended aslimitations on the scope of the present invention.

That which is claimed is:
 1. A method of sheeting water on a surfacecomprising applying to the surface before the surface is exposed towater a polish formulation containing as components thereof at least onemember selected from the group consisting of waxes, solvents,surfactants, thickening agents, abrasives, dyes, odorants, and otheringredients normally used in making polishes, the polish formulationincluding therein a zwitterionometric composition which is the reactionproduct of an acid anhydride and an aminofunctional siloxane selectedfrom the group consisting of (A) a combination of a hydroxyl endblockedpolydimethylsiloxane having a viscosity in the range of about 10 to15,000 cs at twenty-five degrees centigrade, and a silane selected fromthe group consisting of those having the general formulae R"_(n)(R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n) (R'O)_(3-n) SiRNHCH₂ CH₂ NH₂wherein R"' is a hydrogen atom or a methyl radical, R" is a monovalenthydrocarbon radical free of aliphatic unsaturation and contains from oneto six carbon atoms, n has a value of from zero to two, R' is an alkylradical containing from one to four carbon atoms, and R is a divalenthydrocarbon radical free of aliphatic unsaturation and contains three tofour carbon atoms, (B) a combination of a hydroxyl endblockedpolydimethylsiloxane having a viscosity in the range of about 10 to15,000 cs at twenty-five degrees centigrade, a silane selected from thegroup consisting of those having the general formulate (R₁ O)₃ --SiR₂NHR₃ and (R₁ O)₃ --SiR₂ NHCH₂ CH₂ NH₂ wherein R₁ is an alkyl radicalcontaining from one to four carbon atoms, R₂ is a divalent hydrocarbonradical free of aliphatic unsaturation and contains from three to fourcarbon atoms, and R₃ is selected from the group consisting of thehydrogen atom and the methyl radical, and a silane having the generalformula X₃ SiZ wherein X is selected from the group consisting of alkoxyand acyloxy radicals containing from one to four carbon atoms, and Z isa nonhydrolyzable radical selected from the group consisting ofhydrocarbon radicals, halogenated hydrocarbon radicals, and radicalscomposed of carbon, hydrogen, and oxygen atoms, wherein the oxygen atomsare present in hydroxyl groups, ester groups, or ether linkages, therebeing from one to ten carbon atoms in the Z radical, and (C) acombination of a polydimethylsiloxane having a viscosity in the range ofabout one to 15,000 cs at twenty-five degrees centigrade, and a silaneselected from the group consisting of those having the general formulaeR"_(n) (R'O)_(3-n) Si(CH₂)₃ NHR"' and R"_(n) (R'O)_(3-n) SiRnHCH₂ CH₂NH₂ wherein R"' is a hydrogen atom or a methyl radical, R" is amonovalent hydrocarbon radical free of aliphatic unsaturation andcontains from one to six carbon atoms, n has a value of from zero totwo, R' is an alkyl radical containing from one to four carbon atoms,and R is a divalent hydrocarbon radical free of aliphatic unsaturationand contains three to four carbon atoms.
 2. The method of claim 1wherein the acid anhydride is selected from the group consisting ofsuccinic anhydride, maleic anhydride, phthalic anhydride, and carbondioxide.
 3. The method of claim 2 wherein the reaction product is anaminofunctional siloxane zwitterion having the structural formula:##STR7## where Me is methyl, x is an integer of from about forty toabout four hundred, y is an integer of from about one to about twenty,and R₄ is ethylene, vinylidene, or phenylene.
 4. The method of claim 3wherein x is preferably 188 and y is ten.
 5. The method of claim 3wherein the zwitterionic aminofunctional siloxane is further reactedwith a strong acid resulting in an equilibrium of the zwitterion and aconjugate acid base pair of the zwitterion and the acid which dependsupon the pKa of the strong acid and the dielectric strength of thesolvent.
 6. The method of claim 5 wherein the strong acid is selectedfrom the group consisting of hydrochloric, hydrobromic, hydriodic,nitric, perchloric, phosphoric, and organic acids.
 7. The method ofclaim 6 wherein the organic acid is selected from the group consistingof acetic, propionic, butyric, valeric, caproic, benzoic,halo-substituted benzoic, and nitro-substituted benzoic.
 8. The methodof claim 5 wherein the conjugate acid base pair of zwitterion and thestrong acid has the structural formula: ##STR8## where Me is methyl, xis an integer of from about forty to about four hundred, y is an integerof from about one to about twenty, A is an anion, and R₄ is ethylene,vinylidene, or phenylene.
 9. The method of claim 8 wherein x ispreferably 188 and y is ten.